Lanthanides: Properties and Reactions

Lanthanides general properties (Lanthanides share the following

common properties):
• The lanthanides are located in block 5d of the periodic table.
• Lanthanides are soft metals with a silvery white colour.
• their hardness increases across the series.
• They have high melting points ranging from 1000K to 1200K (Except
Samarium, 1623K).
• Lanthanides are good conductors of heat and electricity.
• The lanthanides are strongly paramagnetic.
• They are non-radioactive in nature except Promethium
• A decrease in atomic and ionic radii from lanthanum to lutetium is observed.
This is called the lanthanoid contraction.
• Burn easily in air.
• They are strong reducing agents.
• Their compounds are generally ionic.
• At elevated temperatures, many rare earths ignite and burn vigorously.
• The lanthanides react readily with most nonmetals and form binaries on
heating with most nonmetals.
• The coordination numbers of lanthanides are high (greater than 6; usually 8
or 9 or as high as 12).
• Tendency to decreasing coordination number across the series.
• Difficulty in separating lanthanides: Because the ionic radii of Lanthanides
differ only slightly, their chemical characteristics are comparable. This makes
element separation in the pure state challenging.

Physical Properties
1. Among the inner transition series, the density trend will be the inverse
of atomic radii were (density is the ratio of a substance’s mass to its
volume), i.e. density will grow as the atomic number increases over the
period. They have a high density that ranges from 6.77 to 9.74 g cm -3. It
rises as the atomic number rises.

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 2. Lanthanides have a relatively high melting point, but there is no
discernible pattern in their melting and boiling points.
3. Magnetic Properties: Materials are classed as diamagnetic if they are
repelled by a magnetic field and paramagnetic if they are attracted by
one. Because of unpaired electrons in orbitals, lanthanide atoms/ions
other than f0 and f14 are paramagnetic in nature. As a result, Lu 3+, Yb2+,
and Ce4+ are diamagnetic.
4. Ionization energy is meaning the amount of energy required to remove a valence
electron from an atom in gas phase. From that we see from the table the ionization
energy increase across the series but it decreases in some metals according to the
natural of it.

Chemical Properties Of (+III) Compounds

1- Radii of tripositive lanthanide ions
The size of the atomic and ionic radii is determined by both the nuclear charge
and by the number of electrons that are in the electronic shells. Within those

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 shells, the degree of occupancy will also affect the size. In the Lanthanides, the
size of M3+ ions decreases as we move through the lanthanides from lanthanum
to lutetium. This steady decrease in ionic radii of M3+cations in the lanthanide
series is called Lanthanide contraction.
Cause of lanthanide contraction

The lanthanide contraction is due to the imperfect shielding of one 4f electron by

another in the same sub shell. As we move along the lanthanide series, the nuclear
charge and the number of 4f electrons increase by one unit at each step. However,
due to imperfect shielding, the effective nuclear charge increases causing a
contraction in electron cloud of 4f-subshell.
(In case of lanthanide elements , it has been experimentally found that with
increasing atomic number, the atomic and ionic size of lanthanide
elements gradually decreases from lanthanum to lutetium. It is very much regular
for lanthanide ions ( Ln 3+) . It will be seen that on going from La 3+ to Lu 3+, the
ionic radius shrinks from 115 pm to 93 pm . The steady decrease in ionic radius all
along the series amounting in all to 22 pm , is called lanthanide contraction . )

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 The shielding or screening effect of ‘f’-orbital is very much less than ‘s’, ‘p’ even than
that of ‘d’-orbital. This is due to the shape of ‘f’-orbital. Hence the effective nuclear charge
increases by one at each step. Consequently, the inward pull experienced by the 4f electrons
increases. As a result, the size of the entire 4f n shell reduces. The sum of the successive reductions
gives the lanthanide contraction .

2- Basicity
Basicity is a measure of the ease at which an atom will lose electrons. In another
words, it would be the lack of attraction that a cation has for electrons or anions. In
simple terms, basicity refers to have much of a base a species is. For the Lanthanides,
the basicity series is the following:

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 La3+ > Ce3+ > Pr3+ > Nd3+ > Pm3+ > Sm3+ > Eu3+ > Gd3+ > Tb3+ > Dy3+ > Ho3+ >
Er3+ > Tm3+ > Yb3+ > Lu3+
In other words, the basicity decreases as the atomic number increases

3- Metals and their Alloys

The metals have a silvery shine when freshly cut. However, they can tarnish quickly
in air, especially Ce, La and Eu. These elements react with water slowly in cold,
though that reaction can happen quickly when heated. This is due to their
electropositive nature. The Lanthanides have the following reactions:
• oxidize rapidly in moist air
• dissolve quickly in acids
• reaction with oxygen is slow at room temperature, but they can ignite around
150-200 °C
• react with halogens upon heating
• upon heating, react with S, H, C and N
4- Complex formation:
Lanthanides with 3+ oxidation states have a greater charge to radius ratio.
Lanthanides’ ability to form complexes is thus reduced when compared to d-block
elements. the tendency to form complex and their stability increases with increasing
atomic number. Nonetheless, they form compounds with powerful chelating agents
such as EDTA, -diketones, oxime, and so on. They are not capable of forming P-
complexes.
Lanthanides, owing to the unavailability of orbitals for bonding, high basicity and
larger size of their common cation Ln3+, form few complexes which are mostly with
oxygen or O2 plus N2 containing chelating ligands such as, β-diketones, hydroxo
acids (e.g. tartaric acids or citric acids) various amino acids of the type
RN(CH2COOH)2 and N(CH2COOH)3, EDTA, oxine, (e.g. [Ln(β-diketone)3].H2O.
5- Formation of Coloured Ions
The color that a substance appears is the color that is reflected by the substance. This
means that if a substance appears green, the green light is being reflected. The
wavelength of the light determines if the light with be reflected or absorbed.
Similarly, the splitting of the orbitals can affect the wavelength that can be absorbed.
This is turn would be affected by the number of unpaired electrons.
• The colour of several lanthanide metals is silver-white.

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 • Lanthanide ions with an oxidation state of +3 appear coloured in both solid
and aqueous solutions.
6- Chemical Reactivity
The reactivity of all lanthanides is similar; however, it is larger than that of the
transition elements. This is owing to the outer 5s, 5p, and 5d orbitals protecting
unpaired electrons from the inner 4f-orbital. Except for CeO2, which interacts with
hydrogen to generate solid hydrides at 300-400 C, the oxides of M2O3 are easily
tarnished with oxygen. Water breaks down hydrides. Heat the metal with halogen
or the oxide with ammonium halide to produce halides. Fluorides are insoluble, but
chlorides are deliquescent. Nitrates, acetates, and sulphates are soluble in water,
but carbonate, phosphate, chromates, and oxalates are not.
Chemical Reaction

• The metals are all soft and silvery white.

• They are electropositive and therefore they are very reactive.

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 • The heavier metals are less reactive than the lighter ones because they form a
layer of oxide on the surface.
• The chemical properties of the group are essentially the properties of trivalent
ionic compounds.
• The lanthanides are all much more reactive than is Al and are slightly more
reactive than Mg.

1- Reaction with water

Lanthanides react slowly with cold water, but more rapidly on heating.

• The hydroxides Ln(OH)3 are precepted from aqueous solution by NH4OH

as gelatinous precipitate which are ionic and basic than the amphoteric
Al(OH)3.

• They absorb CO2 from air and form carbonates.

• The basicity decreases as the ionic radius decrease from Ce Lu

• Ce(OH)3 is the most basic.
• Lu(OH)3 is the least basic (acidic).
• Ionic radius decrease from left to right [Basic character decrease].

2- Reaction with air

Lanthanum tarnishes slowly in air, and burns readily.
Combustion of lanthanoids in presence of oxygen, gives lanthanide oxide (Ln 2O3).
The one exception is Ce which forms CeIVO2 rather than Ce2O3.

Also forming LnN, at 450°C.

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 • LnN is hydrolyzed by water.

3- Reaction with Hydrogen

The metals react with H2, but often require heating up to 300-400°C to start the
reaction. The products are solids of formula LnH2 which are black, metallic and
conduct electricity.

[ stable to heat, decomposed by water and react by oxygen to form hydroxides]

The hydrides are remarkably stable to heat often up to 900°C. They are
decomposed by water and react with oxygen.

4- Reaction with Halogens

1) The anhydrous halides LnX3
• can be made by heating the metal and halogen
• Or by heating the metal oxide with ammonium halides

2)The fluorides can be precipitated from solution of Ln+3 by addition of F- or HF

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3) The chlorides

• The chlorides are soluble and crystalized with 6 or 7 H2O molecules, if these are
heated, they form oxo halide except Ce give CeO2.

• The bromides and iodides are similar to the chlorides

• At elevated temperatures the metals also react with N, P, As, Sb and Bi,
giving LnN etc.
OXIDATION STATE (+IV)

The only (+IV) lanthanide which exists in solution and has any aqueous
chemistry is Ce4+. The high charge on the ion leads to it being heavily hydrated.
Ce(+IV) solutions are widely used as an oxidizing agent in volumetric analysis
instead of KMnO4 and K2Cr2O7. The common compounds are CeO2 (white
when pure) and CeO2.(H2O)n (a yellow gelatinous precipitate). CeO2 can be
obtained by heating the metal, or Ce(OH)3 in air. It is insoluble in acids and
alkalis, but dissolves if reduced, giving Ce3+ solutions. A number of complexes
are stable, for example ceric ammonium nitrate (NH4)2[Ce(NO3)6].

• The elements Pr, Nd, Tb and Dy also form (+IV) states. These are generally
unstable, occur only as solids, and are found as fluorides or oxides which may
be nonstoichiometric.

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OXIDATION STATE (+II)

• The only (+II) states which have any aqueous chemistry are Sm2+, Eu2+
andYb2+.
• The most stable divalent lanthanide is Eu2+. This is stable in water, but
the solution is strongly reducing.
• Eu+3 solution can be reduced by Na, Mg , Zn or zinc amalgam to Eu+2.
•
• In number of ways Eu+2 resembles Ca+2 {in solubility of SO4 and
Carbonate}
• EuSO4 , EuCO3 → IN SOLUBLE
• EuCl2 insoluble in HCl and soluble in liquid ammonia
• The states Nd(+II), Pm(+II), Sm(+II) and Gd(+II) are only found in solid
dihalides LnCl2 and LnI2.

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